CN103930648A - 使用甘露聚糖水解酶酶破胶剂压裂的方法 - Google Patents
使用甘露聚糖水解酶酶破胶剂压裂的方法 Download PDFInfo
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Abstract
嗜热甘露聚糖水解酶可被用作用于压裂液的酶破胶剂,所述压裂液含有瓜尔胶及未衍生的瓜尔胶的可水合的聚合物。甘露聚糖水解酶的氨基酸序列与SEQ ID NO:2的氨基酸序列具有至少90%同源性。
Description
【技术领域】
在超过160℉的温度下水解半乳甘露聚糖底物的分离的甘露聚糖水解酶在含有瓜尔胶及衍生的瓜尔胶的压裂液中作为酶破胶剂(enzyme breaker)具有特定可应用性。
【背景技术】
液压压裂用于产生从钻孔延伸进岩层的地下裂缝,以便增加压裂液可由地层(subterranean fracture)产生的速度。一般而言,将高粘度压裂液以足够的压力泵入井,以断裂地层。为了维持增加的暴露于地层,将固体支撑剂加入被通过施加到压裂液的高压携带到裂缝的压裂液。
大于65%的常规压裂液是由瓜尔胶(半乳甘露聚糖)或瓜尔胶衍生物诸如羟丙基瓜尔胶(HPG)、羧甲基瓜尔胶(CMG)和羧甲基羟丙基瓜尔胶(CMHPG)制成。这些聚合物可被交联,以便增加它们的粘度和增加它们的支撑剂运输的能力。
一旦高粘度压裂液将支撑剂携带到了地层,使用破胶剂减小压裂液的粘度,其允许支撑剂沉降到裂缝和由此增加地层暴露于井。破胶剂通过减少聚合物分子量,由此‘断裂’聚合物来工作。然后裂缝成为待产生返回到井的流体和气体的高通透性导管。
化学氧化剂和酶最通常被用作破胶剂。氧化剂产生自由基,其然后降解聚合物。此反应限制受限于氧化剂是化学计量的,且它们不仅会攻击聚合物,而且会攻击可被氧化的任何分子。另一方面,酶是催化性和底物特异性的,并会催化聚合物上特定键的水解。酶会在其有寿命期间降解许多聚合物键。不幸的是,酶在窄温度范围内操作,且它们的功能状态常常被高温灭活。
用以降解半乳甘露聚糖的常规酶在环境~中等温度(75℉~150℉)工作良好。在升高的温度,(>150℉)这些酶快速变性及失去活性。常规酶制剂中使用的β-甘露聚糖酶具有约150℉的温度上限。活性特征指示,过了此点,则酶保留少到无活性。因为许多井下压裂操作在超过150℉的温度进行,具有可在这些升高的温度下降解基于瓜尔胶的压裂液的酶会有益。
【发明概述】
甘露聚糖水解酶有效水解半乳甘露聚糖,且在升高的温度范围的瓜尔胶聚合物水解中具有特定有效性。高温甘露聚糖水解酶可关联于谷胱甘肽S-转移酶(GST)或可未关联于GST。
编码甘露聚糖水解酶的核苷酸序列源于解糖热纤维菌(Caldocellum saccharolyticum)的β-甘露聚糖酶基因,并经密码子优化而用于在大肠杆菌(E.coli)中表达。编码甘露聚糖水解酶的基因(下文“htβ”)具有图1A所示的核苷酸序列(SEQ ID NO:1),其被密码子优化而增加甘露聚糖水解酶在大肠杆菌(E.coli)中表达。然后可将基因htβ(SEQ ID NO:1)克隆进适合的质粒载体,诸如pUC57,pUC19,及pGS-21a或克隆进任何其他可商购的载体或自定义表达的载体或克隆载体。可将甘露聚糖水解酶转化进可商购的大肠杆菌(Escherichia coli)株,并在其中表达。甘露聚糖水解酶的翻译的氨基酸序列显示于图1B(SEQ ID NO:2)。
然后可制备水性压裂液,其含有酶,瓜尔胶聚合物及交联剂。
当在液压压裂中使用时,甘露聚糖水解酶对于在超过160℉的温度降解基于瓜尔胶的聚合物中有效。
【附图说明】
为了更完全地理解,本发明的详述中参照图,提供各图的简述,其中:
图1A(SEQ ID NO:1)显示本发明中使用的编码甘露聚糖水解酶的核苷酸序列。图1B(SEQ ID NO:2)显示甘露聚糖水解酶的氨基酸序列。
图2显示带有甘露聚糖水解酶基因的质粒pUC57-htβ,pGS-21a-gst-htβ和pGS-21-htβ的构建。
图3对比了于180℉的25ppt的含有甘露聚糖水解酶的硼酸盐交联的瓜尔胶悬浮液对比不含有甘露聚糖水解酶的悬浮液18小时之后的粘度减小。
图4对比了于160℉的25ppt的含有甘露聚糖水解酶的硼酸盐交联的瓜尔胶悬浮液对比不含有甘露聚糖水解酶的悬浮液18小时之后的粘度减小。
图5对比了于180℉的含有甘露聚糖水解酶的硼酸盐交联的瓜尔胶悬浮液对比不含有甘露聚糖水解酶的悬浮液经10小时的粘度减小。
图6对比了于140℉的含有甘露聚糖水解酶的硼酸盐交联的瓜尔胶悬浮液对比不含有甘露聚糖水解酶的悬浮液经3.5小时的粘度减小。
图7对比了不同温度的含有甘露聚糖水解酶的瓜尔胶悬浮液的粘度减小。
图8A显示在甘露聚糖水解酶缺失下制造的支撑剂填充层的显微照片。
图8B显示在甘露聚糖水解酶存在下制造的支撑剂填充层。
【优选实施方案详述】
本发明的压裂方法中使用的高温酶,当其未与谷胱甘肽S-转移酶(GST)关联时称之为“甘露聚糖水解酶”,而当其是β-甘露聚糖酶和GST的融合体时称之为“GST-甘露聚糖水解酶”。
本文所述的甘露聚糖水解酶来源于嗜热和厌氧解糖热纤维菌。编码β-甘露聚糖酶的基因的分离描述于E.Luthi et al,“Cloning,Sequence Analysis,and Expression in Escherichia coli of a GeneCoding for aβ-Mannanase From the Extremely ThermophilicBacterium‘Caldocellum saccharolyticum’,Applied andEnvironmental Microbiology,Mar.1991,pp.694-700,其通过引用并入本文。
甘露聚糖水解酶的基因然后经密码子优化而增加其在大肠杆菌(E.coli)中的表达效率。htβ基因的核苷酸序列如图1A所示(SEQ IDNO:1)。此核苷酸序列与Luthi等人对甘露聚糖酶基因的图2中描绘的序列具有74%同源性。核苷酸序列包括甘露聚糖水解酶的编码序列和N-端的前导序列。
如图2(a)所示,可将htβ基因克隆进克隆载体pUC57而产生质粒pUC57-htβ。在(b)及(c)中,可将基因克隆进含有GST蛋白的编码区的表达载体pGS-21a。在(b)中,得到的基因编码GST-甘露聚糖水解酶融合产物。在(c)中,得到的基因编码无GST融合标签的酶。分别使用(b)和(c)的pGS-21a-gst-htβ和pGS-21a-htβ质粒的表达分别产生与N-端GST蛋白融合的甘露聚糖水解酶和无关联的GST蛋白的甘露聚糖水解酶。
在各图2(a),(b)及(c)中,Ampr调控β-内酰胺酶的表达,rep(pMB1)和f1ori分别代表pUC57和pGS-21a中的复制原点,负责质粒的复制,lacI编码乳糖阻遏物,T7代表T7RNA聚合酶启动子,MCS代表多克隆位点。优化的序列的5’端含有BamHI限制性内切酶位点,3’端含有HindIII限制性内切酶位点,其用于克隆进pGS-21a表达载体而产生GST-甘露聚糖水解酶融合蛋白。或者,5’BamH1位点用NdeI限制性内切酶位点取代而产生无关联的GST融合的甘露聚糖水解酶蛋白。
质粒pGS-21a-htβ、pGS-21a-gst-htβ和pUC57-htβ可转化进可商购的大肠杆菌(E.coli)菌株及培养。然后可收获细胞,裂解,将得到的溶液用作细胞裂解物。可通过自裂解产物移出细胞碎片来产生无细胞的提取物,然后可从提取物分离酶。术语“分离的”表示酶已从完整细胞或细胞碎片移出,在非其天然环境的条件下,无其他外来的或不需要的核酸、蛋白酶和脂质,取适合用作压裂液的破胶剂的形式。
编码甘露聚糖水解酶的基因可还具有与图1A的核苷酸序列(SEQID NO:1)基本上同源的核苷酸序列。术语“基本上同源”在本文用来表示与图1中显示的序列(SEQ ID NO:1)具有至少75%、更优选至少80%、更优选至少85%、甚至更优选至少90%的序列同一性的核苷酸。
甘露聚糖水解酶的翻译的氨基酸序列显示于图1B(SEQ ID NO:2)。一般而言,本文所述的液压压裂方法中使用的甘露聚糖水解酶的翻译的氨基酸序列至少60%类似于图1B所示的翻译的氨基酸序列(SEQ ID NO:2)。
在优选的形式中,分离的蛋白基本上无其他蛋白。提供大于40%纯形式、更优选大于60%纯形式的蛋白是优选的。甚至更优选,提供高度纯化的形式,即,如通过SDS-PAGE测定的大于80%纯、更优选大于95%纯、甚至更优选大于99%纯的蛋白是优选的。
甘露聚糖水解酶在升高的温度范围,诸如超过72℉,一般在约5.0~约11.0之间的pH范围有效水解瓜尔胶聚合物。甘露聚糖水解酶可在超过160℉以及超过180℉的温度水解瓜尔胶聚合物。实际上,甘露聚糖水解酶可在超过185℉和甚至超过195℉的温度水解瓜尔胶聚合物。此外,甘露聚糖水解酶可用于与其他酶和/或氧化破胶剂组合而在更广温度和pH范围降解瓜尔胶凝胶。
本发明中使用的水性压裂液可通过将可水合的聚合物与水性流体混合来制备。水性流体可为,例如,水,盐水或水-醇混合物。任何适合的混合设备可用于此过程。在分批混合的情况中,将可水合的聚合物和水性流体混合足以形成水合的溶胶的时间。将可水合的聚合物以水性流体的重量计约0.10%~5.0%的浓度加入水性流体。对于本发明最优选的范围是以重量计约0.20%~0.80%。压裂液的pH可通常为约5.0~约11.0,一般约6.0或更高,更一般约6.5或更高。在一实施方式中,压裂液的pH可为约7.0或更高或约7.5或更高。在另一实施方式中,压裂液的pH可为约8.0或约8.5或更高。在优选的实施方式中,压裂液的pH大于或等于9.0和更优选大于或等于约9.5。
在本发明中可用的可水合的聚合物是未衍生的瓜尔胶以及衍生的瓜尔胶。优选未衍生的瓜尔胶。衍生的瓜尔胶的例包括羟丙基瓜尔胶、羧甲基羟丙基瓜尔胶及羧甲基羟乙基纤维素。
除了酶破胶剂和可水合的聚合物之外,压裂液包括交联剂。交联剂可为含金属离子的聚合物,其包括铝,锑,锆,和含有钛化合物,其包括,所谓的有机钛酸盐,以及硼酸盐和释放硼的化合物。在硼酸盐交联剂的情况中,交联剂是供给硼酸根离子的任何物质。适合的硼酸盐交联剂包括有机硼酸盐,单硼酸盐,多硼酸盐,矿物质硼酸盐,硼酸,硼酸钠,包括无水或任何水合物,硼酸盐矿石,诸如硬硼酸钙石或钠硼解石,以及与有机化合物复合而延迟硼酸根离子释放的任何其他硼酸盐。优选硼酸盐交联剂。
交联剂优选以水性流体的重量计从约0.001%至超过0.5%的范围存在。优选地,交联剂浓度在以水性流体的重量计约0.005%~约0.25%的范围内。
一般而言,酶作为酶水溶液引入。处理液中的酶溶液的重量百分比依赖于酶水溶液中的酶活性单位数。例如,处理液中具有30,000U的酶活性的酶水溶液的量通常在约0.05~约1.3重量百分比之间,优选约0.103~约0.206重量百分比之间。含有不同酶活性单位的酶溶液的重量百分比可使用含有30,000U的酶活性的酶溶液的指定的重量百分比测定。
含有可交联的聚合物的水性流体的最佳pH是碱性的,且一般在约9.5~约11.0之间。
本发明的压裂液也可具有作为伴侣物质掺入酶破胶剂的pH调节物质。pH调节物质是起初惰性,但在胶凝的压裂液中缓慢水解而产生Bronsted酸,由此逐渐降低胶凝的流体的pH及活化酶破胶剂的任何物质。优选的pH调节物质包括缓慢水解而产生Bronsted酸的有机酐,酰基卤,磺酰卤,苄型卤化物和低分子量酯。"低分子量"酯是指应在压裂液中可溶性,以便实现旨在的经时水解而产生酸的目的的酯。一般而言,分子量越高,酯越不可溶。结果,更低分子量酯优选容易使用。优选地,pH调节物质是低分子量酯选自:乙基乙酸酯,2-乙氧基乙基乙酸酯,乙基乙酰乙酸酯,三乙基柠檬酸酯,甲基苯甲酸酯和二甲基酞酸酯。以下实施例中使用的2-乙氧基乙基乙酸酯,乙基乙酰乙酸酯和三乙基柠檬酸酯的典型分子量分别是132、130和276。优选地,pH调节物质以水性流体的重量计约0.01%~约0.85%的范围内存在。
井处理液可使用高剪切泡沫发生器原位制备或可航运到期望的位置。
压裂液可还含有在添加交联剂之前正常添加到压裂液的支撑剂。一旦由压裂液运输进地层,可在产生的或扩大的裂缝内形成支撑剂的包装,以保持裂缝在自地层产生流体期间打开。支撑剂填充层能在裂缝中形成支撑剂的部分单层而在邻接支撑剂粒子之间提供增加的互连的间质空间是期望的。由于产生的流体一般围绕宽间隔的支撑剂粒子流动而非流过填充床中的间质空间,导致裂缝导通性增加。
在一方面,压裂液中的支撑剂的量可在约0.5~约12.0(磅支撑剂/加仑压裂液)之间。优选地,其可在约0.25~约4.0镑/加仑压裂液之间。
适合的支撑剂包括本领域常规知道的那些,包括石英砂粒,玻璃珠,铝沉淀,陶瓷,塑料珠,包括聚酰胺和超轻型(ULW)粒子,诸如坚果如胡桃,椰子,美国山核桃,杏仁,象牙果,巴西栗,等的研磨或压碎的壳;果实诸如李子,橄榄,桃,樱桃,杏,等的种子的研磨和压碎的种壳(包括果核);其他植物诸如玉米(例如,玉米轴或玉米仁),等的研磨和压碎的种壳;处理的木材,诸如源于木材诸如栎、山核桃、胡桃、杨、桃花心木等的那些,包括已通过研磨、削或其他形式的粒子化、处理、等处理的木材。
其他支撑剂可包括多孔陶瓷或有机聚合物粒子。多孔颗粒物可用非-多孔穿透物质、涂覆层或上釉层处理。例如,多孔颗粒物可为处理的颗粒物,如美国专利公开No.20050028979中定义的,其中(a)处理的多孔材料的ASG小于多孔颗粒物的ASG;(b)处理的材料的通透性小于多孔颗粒物的通透性;或(c)处理的材料的空隙度小于多孔颗粒物的空隙度。
支撑剂正常以约1~8镑之间/加仑的压裂液组合物的浓度使用,但可根据需要使用更高或更低浓度。
压裂液也可含有修井工业常见的其他常规添加剂,诸如表面活性剂、腐蚀抑制剂、交联延迟剂等。
在典型压裂操作中,本发明的压裂液以足够高压泵出,以导致裂缝的形成或放大,并将支撑剂放到裂缝中。
下列实施例是本发明的一些实施方式的例证。除非另外指示,实施例中出现的全部百分比以重量单位给出。
【实施例】
【实施例1】
将htβ基因克隆进克隆载体pUC57而产生质粒pUC57-htβ及克隆进表达载体pGS-21a而产生pGS-21a-htβ质粒。然后将质粒pGS-21a-htβ和pUC57-htβ转化进感受态BL21(DE3)或DH5α大肠杆菌(E.coli)株,并在5mL LB-Miller营养培养基中,于98.6℉,以200rpm培养16小时。向培养肉汤补充100μg/mL氨苄西林,将其用作带有质粒pGS-21a-htβ或pUC57-htβ的大肠杆菌(E.coli)的100mL培养物的接种物。这些培养物于98.6℉和200rpm培养。4小时之后,将异丙基β-D-1-硫代吡喃半乳糖苷(IPTG)加入培养至终浓度0.1mM。IPTG存在下3小时的温育之后,将细胞冷却到39℉,并通过以3,000rpm离心20分钟来收获。然后去除培养基,并将细胞于-4℉存储直到使用。然后将细胞解冻及重悬浮于5mL冷却的50mM磷酸钠缓冲剂。以1mg/mL的终浓度加入溶菌酶,并将培养物于室温温育30分钟。将核酸通过超声处理的短暂脉冲破坏,并通过离心获得产生的无细胞的提取物(CFX)。
【实施例2】
将约1gpt的作为GBW-12CD从Baker Hughes公司可商购的常规β-甘露聚糖酶,以1:33体积测定比在水中稀释,并将约2mL的含有pGS-21a-htβ和pUC57-htβ的实施例1的CFX添加到含有25pptGW3、2gpt BF-7L和1gpt XLW-32的100mL水性流体,并于180℉温育18小时。(GW-3是瓜尔胶悬浮液剂,XLW-32是硼酸盐交联剂,及BF-7L是缓冲剂,全部可从Baker Hughes公司商购)。然后允许样品冷却到室温,并使用Fann35粘度计测量它们的粘度。结果显示于图3,其中显示,于180℉在18小时之后甘露聚糖水解酶提供几乎完全瓜尔胶粘度减小,而常规酶产物不呈现在此温度和pH减少交联的流体的粘度中有效。图3中的箭标代表未断裂的样品。全部样品的初始pH是10.5。
【实施例3】
将约1gpt的实施例3的常规酶及2mL自来自实施例1的含有pGS-21a-htβ和pUC57-htβ的样品的CFX添加到100mL含有25pptGW-3,2gpt BF-7L和1gpt XLW-32的水性样品,并于160℉温育18小时。在pH6.5和10.5使用GW-3的样品。常规酶,GBW-12,显示在pH6.5但不在10.5降解GW-3样品。含有甘露聚糖水解酶的样品于160℉18小时之后提供交联的GW-3的部分至完全降解。在Fann35上测量粘度,并显示于图4,其中图4代表硼酸盐交联的25ppt GW-3被甘露聚糖水解酶的粘度减小。箭标代表未破胶的样品。
【实施例4】
制备100mL水性流体而含有25ppt GW3、1.5gpt BF-7L和1.5gpt的从Baker Hughes公司作为XLW-30可商购的在烃油中制浆的硼酸盐矿石交联剂。溶液的pH是10.8。然后制备2个样品。一个样品,指定为(-),无酶添加到流体。其他样品,指定为(+),具有0.75gpt的由pGS21a-htβ表达载体产生的甘露聚糖水解酶CFX溶液的1/25稀释。图5代表于180℉经10小时的2个样品的粘度减小。图6代表于140℉经10小时的2个样品的粘度减小。
【实施例5】
制备100mL水性流体而含有25ppt GW3,1.3gpt BF-7L和1.0gpt XLW-32交联剂用于于72℉和140℉测试。制备第2100mL水性流体而含有25ppt GW3,2.0gpt BF-7L和1.5gpt XLW-30交联剂用于于200℉测试。在全部样品中,甘露聚糖水解酶浓度是0.5gpt。在Chandler HTHP5550粘度计上以100s-1测量各样品的流变学。图7代表在可变的温度的测试的流变学特征,并展示,甘露聚糖水解酶在从72℉到至少200℉的一系列温度下,减少交联的半乳甘露聚糖聚合物的粘度中有效。
实施例2、3、4和5展示,含有甘露聚糖水解酶的压裂液在常规酶不那么有效的升高的温度和pH范围有效水解瓜尔胶聚合物。
【实施例6】
此实施例例证用含有甘露聚糖水解酶破胶剂的水性流体处理的支撑剂填充层的重获的传导性。制备100mL水性流体的2个样品而含有25ppt GW-3、1.5gpt BF-7L和1.3gpt XLW-30。一个样品还含有1.25gpt(1/5稀释)的甘露聚糖水解酶(参考实施例6);其他样品未含有任何酶。60mL注射器装备有切成注射器内径的30目网筛。所述网筛支持一片过滤纸(2.5μm孔径),其也切成注射器内径。然后将10g的20/40CarboProp,Carbo Ceramics的支撑剂应用于过滤纸。然后将100mL交联的流体应用于支撑剂床,及通过支撑剂填充层施力,直到柱塞静止在支撑剂填充层顶部。在注射器端封头,并将注射器浸没到180℉水浴24小时。然后自水浴移出注射器,并允许冷却到室温。然后将注射器倒置,并将柱塞轻轻移出,以最小化对支撑剂填充层的干扰。将支撑剂填充层放入蓝称量盘,并立即在复合光学显微镜下用10×放大率可视化。图8A和8B是支撑剂填充层的显微照片,例证不含有甘露聚糖水解酶的悬浮液(显微照片A)对比含有甘露聚糖水解酶的悬浮液(显微照片B)之间的传导性。
如显示于显微照片A,支撑剂填充层具有高度定义的结构,表示压裂液保持交联。(自注射器的其余流体也交联)。显微照片B显示无结构的支撑剂填充层,其中填充层自注射器移出后立即“崩溃”。自注射器的其余流体像水-样,具有非常低的粘度。自含有甘露聚糖水解酶的压裂液的支撑剂填充层显示残留少至无交联的凝胶。此提示,支撑剂填充层通透性的优良的净化和高恢复。
【实施例7】
此实施例例证在10升发酵过程中甘露聚糖水解酶的产生。将htβ基因用限制性内切酶NdeI和HindIII克隆进表达载体pGS21-a而产生无关联的GST融合的甘露聚糖水解酶。将得到的表达载体转化进BL21(DE3)大肠杆菌(E.coli),并平铺于含有100μg/mL氨苄西林的LB-琼脂板。将板于98.6℉温育过夜。自板挑选单集落及用以接种100mL的含有100μg/mL氨苄西林的LB-Miller肉汤。将培养物于98.6℉以200RPM温育过夜。
将100mL过夜培养物作为接种物放入在来自New BrunswickScientific的Bioflow3000发酵罐中的10L的Terrific肉汤中。以100μg/mL的终浓度加入氨苄西林。将发酵培养物于98.6℉伴随最大搅拌和补给压缩的空气以维持可能的最大通气地生长24小时。将甘油以4mL/小时的速度添加整24小时。根据需要添加消泡剂溶液。一旦OD600达到0.5的值,将无菌乳糖溶液加入混合物,从而系统中的乳糖终浓度是15mM。24小时之后,将细胞培养物于39℉存储,直到进一步处理。
然后将细胞培养物均质化,并将细胞碎片通过离心或经0.2μm孔径聚醚砜膜过滤来移出。然后可将得到的溶液用作甘露聚糖水解酶溶液或根据期望进一步浓缩。在此实施例中,将滤出液经切向流过滤(TFF),使用30,000MWCO聚醚砜滤器浓缩。然后使用渗余物作为甘露聚糖水解酶溶液。
本领域技术人员通过本说明书会明晰本权利要求的范围之内的其他实施方式。希望说明书,以及实施例,仅被认为是例示,本发明的范围和精神由随附权利要求给出。
Claims (20)
1.液压压裂地层的方法,其包括向地层中以足以在地层中产生或放大断裂的压力导入具有约8.5~约11.0的pH的压裂液,所述压裂液包含:
(a)选自下列的可水合的聚合物:未衍生的瓜尔胶及衍生的瓜尔胶;
(b)交联剂,其用于交联可水合的聚合物而形成聚合物凝胶;以及
(c)酶破胶剂,其包含甘露聚糖水解酶,所述甘露聚糖水解酶具有与SEQ ID NO:2的氨基酸序列具有至少90%同源性的氨基酸序列。
2.权利要求1的方法,其中地层的井下温度超过180℉。
3.权利要求2的方法,其中地层的井下温度超过185℉。
4.权利要求1的方法,其中甘露聚糖水解酶具有与SEQ ID NO:2的氨基酸序列具有至少95%同源性的氨基酸序列。
5.权利要求1的方法,其中交联剂含有硼或能向流体提供硼离子。
6.权利要求1的方法,其中可水合的聚合物是未衍生的瓜尔胶。
7.液压压裂由井穿透的地层的方法,其包括:
(a)向井以足以在地层中产生或放大断裂的压力泵入压裂液,所述压裂液包含:
(i)选自下列的可水合的聚合物:未衍生的瓜尔胶及衍生的瓜尔胶;
(ii)交联剂,其用于交联可水合的聚合物而形成聚合物凝胶;
(iii)酶破胶剂,其包含甘露聚糖水解酶,所述甘露聚糖水解酶具有与SEQ ID NO:2的氨基酸序列具有至少90%同源性的氨基酸序列;以及
(iv)支撑剂;以及
(b)在产生的或放大的断裂中产生支撑剂的部分单层。
8.权利要求7的方法,其中地层的井下温度超过160℉。
9.权利要求7的方法,其中可水合的聚合物是未衍生的瓜尔胶。
10.权利要求7的方法,其中甘露聚糖水解酶具有与SEQ ID NO:2的氨基酸序列具有至少95%同源性的氨基酸序列。
11.权利要求10的方法,其中甘露聚糖水解酶具有与SEQ ID NO:2的氨基酸序列具有至少99%同源性的氨基酸序列。
12.液压压裂由井穿透的地层的方法,其中向井以足以在地层中产生或放大断裂的压力泵入压裂液,所述压裂液含有衍生的或未衍生的瓜尔胶,交联剂和酶破胶剂,改良是使用嗜热甘露聚糖水解酶作为酶破胶剂,嗜热甘露聚糖水解酶具有与SEQ ID NO:2的氨基酸序列具有至少90%同源性的氨基酸序列。
13.权利要求12的方法,其中甘露聚糖水解酶具有与SEQ ID NO:2的氨基酸序列具有至少95%同源性的氨基酸序列。
14.权利要求12的方法,其中压裂液的pH在约5.0~约11.0之间。
15.权利要求14的方法,其中压裂液的pH大于或等于6.0。
16.权利要求15的方法,其中压裂液的pH大于或等于6.5。
17.权利要求16的方法,其中压裂液的pH大于或等于7.0。
18.权利要求17的方法,其中压裂液的pH大于或等于7.5。
19.权利要求18的方法,其中压裂液的pH大于或等于8.0。
20.权利要求12的方法,其中可水合的聚合物是未衍生的瓜尔胶,且其中甘露聚糖水解酶具有与SEQ ID NO:2的氨基酸序列具有至少99%同源性的氨基酸序列。
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